Substantive sulfur dye.



UNITED STATES Patented August 11,1903.

PATENT OFFICE.

PAUL JULIUS AND FRIEDRICH REUBOLD, OF LUl)\1VIGSHAFEN-ON-THE- RHINE, GERMANY, ASSIGNORS TO BADISCHE ANILIN & SODA FABRIK, OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

SUBSTANTIVE SULFUR DYE.

SPECIFICATION forming part of Letters Patent No. 735,775, dated August 11, 1903.

Application filed March 16, 1901. Serial No. 51,505. (Specimena) I To (1% whom it may concern.-

Be it known that we, PAUL JULIUS, doctor of philosophy and chemist, a subject of the Emperor of Austria-Hungary, and FRIEDRICH REUBOLD, doctor of philosophy and chemist, a subject of the King of Bavaria, both residing at Ludwigshafen on -the -Rhine, in the Kingdom of Bavaria,Germany,hav e invented new and useful Improvements in Substantive Sulfurized Dyes, of which the following is a specification.

We have discovered that if dinitro meta dichlor-benzene be treated with alkali thiocyanates (also called alkali sulfocyanides in the presence of a suitable solvent or diluent both chlorin atoms are replaced by the thiocyanogen group. This reaction can be effected by allowing mixed solutions of dinitro-dichlor-benzene and potassium thiocyanate to stand for a suflicient time in the cold. Judging from the method of its formation the new product possesses the constitution represented by the following formula:

nolic body and the above di-thiocyan-dinitro benzene, using alcohol as solvent or diluent and at a temperature of from fifty to seventy degrees centigrade in the presence of an agent capable of binding ac,id,such as sodium acetate. In the reaction that takes place one thiocyan group appears to be replaced by the residue of the amido-phenolic body employed. In this way a series ofnew bodies is obtained, which may be represented in their constitutions by the following general formula:

son O2N|/\\| .In this formula X represents the residue of the amido body used in the condensation. As instances of the amido bodies that can be used in carrying out this invention we mention paraamido phenol, para-amido-phenol-ortho-sulfoacid, and para -amido-salacylic acid. Equivalent bodies can be obtained by the use of, for instance, potassium hydrosulfid or of a salt of xanthic acid in condensation with a chlorinated benzene derivative. Thus one molecular proportion of 1.3.4.6 dinitro-dichlorbenzene can be combined with one molecular proportion of para-amido-phenol, and the dinitro chlor para hydroxy diphenylamin thus formed can be treated with ahydrosulfid (either in a separate operation or in the melt) or with a salt of xanthic acid. All of these new bodies are to be regarded as thio derivatives of nitro hydroxy dialphylamin. On suitable oxidation corresponding sulfoacids can be obtained. Hereinafter we apply to potassium hydrosulfid, potassium thiocyanate, and potassium xanthate, as well as all their equivalents, the generic term thionizing agent as including all of them. lVe have further discovered that the said new bodies (thio derivatives of nitro-hydroxy-dialphylamin are particularly well suited for yielding substantive dyes for cotton upon treatment with sulfur and sodium sulfid at a high temperature. tained,usin g the products from the new sulfocyan compound and the amido-phenolic bodies mentioned, dye unmordanted cotton, giving, in the first place, greenish-gray-black shades, but the coloration so obtained changes on exposure to warm air. -This may be effected as follows: Prepare a dye bath by The coloring-matters so ob- A means of our new dye, (sodium sulfid and water suitably work the goods to be dyed in this bath, ring them out and allow them to dry slowly in a drying-room whose temperature is, about sixty (60) degrees centigrade. After treatment in this way the shade is a deep blue, possessing to a high degree fastness against the action of washing and against the action of alkalies and acids.

The following examples will serve to illustrate the manner in which our invention may best be carried into practical efiect; but the invention is not confined to the examples given nor to the conditions therein described. The parts are by weight.

Example 1. Production of meta-dinitrodithiocyan-benzene from dinitro-dichZor-benacne and potassiumthiocyanate.Dissolve about four hundred and seventy-four (474) parts of dinitro-dichlorbenzene in one thousand (1,000) parts of acetone and add three hundred and ninety (390) parts of finely-powdered potassium-thiooyanate. Agitate the mixture at ordinary temperature. In a short time the desired condensation product separates out in the crystalline state, as does also .the potassium -chlorid 'formed. Collect the mixture by filtration, grind it with water in orderto dissolve the potassium-chlorid, filter, wash with water, and dry. This condensation can also be effected in alcoholic solution. In this case it is desirable to heat the solution to about forty (40) to fifty degrees centigrade. Further, other thiocyanates can be used in place of potassium-thiocyanate.

The new diuitro-dithiocyan-benzene thus obtained in the dry and powdered state has a yellowish color and is practically insoluble in water, very slightly soluble in cold benzene or cold alcohol, readily soluble in boiling glacial acetic acid and in hot acetone, and slightly soluble in boiling alcohol. It can be recrystallized from the hot alcoholic solution.

Example 2. Production of ortho-para-din-itro metathiooyan parwhydroxy dd hang L amin from meta-dinitro-dithiocyan enzene and'para-amido-phenol.-M1. together about twohundred and eighty-two (282) parts of dinitro-dithiocyan-benzene, one hundred and ten (110) parts of para-amido-phenol, (in the form of base,)and one hundred and fifty (150) parts of crystallized sodium acetate, and suspend this mixture in two thousand five hundred (2, 500) parts of ethyl alcohol, (containing about ninety-six per cent. of O H OH.) Heat 'the mixture to about sixty to sixty-five degrees oentigrade and maintain the heat for about eight (8.) hours. Then allow the whole to cool and collect the reaction product by filtering. Wash with alcohol,

press, and dry. In the dry and powdered state it is of a red color. With cold concentrated sulfuric acid it gives a brown color,

which becomes green when diluted with water. Itis practically insoluble in cold water what more soluble in boiling benzene. It is soluble in acetone, glacial acetic acid, and in ethyl alcohol when boiled with these solvents.

In a similar way the new condensation products can be obtained when using para-amidophenol ortho sulfoacid, (preferably in the form of its sodium salt,) or paraamido salicylic acid. 1

Example 3. Production of a new coloringmatter.--Mix together three hundred (300) parts of crystallized sodium sulfid, eighty parts of powdered sulfur, and one hundred and fifty (150)parts of water. Heat the mixture in an iron pot standing in an oil bath and furnished with a stirrer. When no further solution takes place, allow the mixture to cool to about forty (40) degrees centigrade, then addgradually,while continuallystirring, one hundred (100) parts of ortho-para-dinitrometa-thiocyan para-hydroxy-diphenylamin, such as can be obtained in the manner de scribed in the foregoing examples. During this addition the temperature should not rise above ninety to one hundred degrees centigrade. Continue stirringthe mixture, and raise the temperature gradually to about one hundred and sixty (160) to one hundred and eighty (180) degrees centigrade, and maintain this heat until the reaction mass is completely dry and can readily be powdered. The product so obtained can be directly used in dyeing cotton in the well-known way for sulfur dyes. In the dry and powdered state it is of a black color. With water it yields a greenish-black colored solution in which an excess of hydrochloric acid produces a blackish fiocoulent precipitate. The coloring-matter is practically insoluble in cold acetone, benzene, glacial acetic acid, and in cold ethyl alcohol. In an analogous manner equivalent coloring-matters can also be obtained from the equivalent condensation products hereinbefore mentioned.

Now what we claim is I 1. The process of making substantive sulfurized dye which consists in treating dinitro-meta-dichlor-benzene successively with a hereinbefore-defined thionizing agent, and an aromatic amido-oxy substance and then melting this result with sulfur and sodium sulfid.

2. The process of making substantive sulfurized dye which consists in melting a heroinbefore-defined thio derivative of nitro-hydroxy dialphylamin with sulfur and sodium sulfid.

3. As a new article of manufacture substantive sulfurized dye which can be made from ortho para dinitro thiocyan-para-hydroxy-diphenylamin, sulfur and sodium sulfid which in the dry and powdered state is of a black color soluble in water in the presence of sodium sulfid giving a greenish-black colored. solution in which an excess of hydrochloric acldproduces ablackish flocculeut preour hands in the presence of two subscribing cipitate, practically insoluble in cold acetone, Witnesses.

benzene, glacial acetic acid and in cold ethyl PAUL JULIUS.

alcohol, and which dyes unmordanted cotton FRIEDRICH REU BOLD. 5 from a bath containing sodium sulfid shades \Vitnesses: 4

which turn blue upon exposure to warm air. JOHN L. HEINKE,

In testimony whereof we have hereunto set MAX BAZLEN. 

